Method and apparatus for manufacturing colored sheeting



Feb. 21, 1961 c. R. ADLER ETAL 2,972,546

METHOD AND APPARATUS FOR MANUFACTURING COLORED SHEETING Filed March a, 1957 2 Sheets-Sheet 1 /l0 colvrllvuous BAs/c SOLU77ON MAKER l 12 HOLD/N6 62 CIRCULAT/NG MIXER T CONTINUOUS ClRCULAT/NG SUPPLY OF THE BASIC SOLUTION A INJECTOR BLENDER B SUPPLY OF ADDITIVE C LINE T0 CASTING MACHINE Fig.1.

GharlesRAdler Lawrence GBarllell INVENTORY WM BY gZ W ATTORNEYS Feb. 21, 1961 c. R. ADLER EIAL 2,972,546

METHOD AND APPARATUS FOR MANUFACTURING COLORED SHEETING Filed March 8, 1957 2 Sheets-Sheet 2 FYI. 9:2

CharlesR.Adler Lawrence (ZBarllett ATTORJVEYS United States Patent i ce I METHOD AND APPARATUS FOR MANUFAC- TURING COLORED SI-[EETING Charles R. Adler and Lawrence C. Bartlett, Rochester,

N.Y., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey Filed Mar. 8, 1957, Ser. No. 644,822 6 Claims. (Cl. 106-196) This invention relates to the manufacture of colored film and sheeting. More particularly, this invention relates to the manufacture of colored photographic film base.

There are a number of purposes for which colored film and sheeting may be used. For example, in Hickman US. Patent No. 1,900,877, there is described the use of colored film base for antihalation purposes. According to this patent, uncolored film base has applied thereto a dye solution. The dye is absorbed on the surface of the film base thereby coloring the film.-

It has also been proposed to premix the film-forming materials (frequently referred to as dope) with the coloring materials in the mixer for the dope. Then the colored mixture is formed into sheeting and film. While such prior art methods of premixing in many instances have exhibited advantages over dyeing the surface, there have also been present some disadvantages. That is, some of the prior art premixing procedures have not provided apparatus and methods whereby suitable distribution of the additive may be accomplished. In other premixing methods the mixing has taken place in the dope preparation. This contaminates substantially all of the equipment parts with the particular color so that it is not convenient to change from one color to another. That is, the cleaning of the equipment for a color change may be rather difficult.

Certain other methods and apparatus have been proposed but they are not regarded as permitting the obtaining of as adequate and uniform color distribution as by the apparatus and method of the present invention. Also, the prior art procedures, particularly the first mentioned' procedure, has the disadvantage in that the resultant colored sheeting may possess comb lines, herring bone lines, orange peel, bubble lines, and the like.

Therefore, the development of a novel apparatus and method'for the manufacture of colored sheeting in an improved manner and of a better quality represents a highly desirable result. After extensive investigation we have found an apparatus and method whereby colored sheeting and film, particularly film for photographic purposes, may be better produced.

This invention has for one object to provide an improved apparatus arrangement for mixing additives, such as coloring materials, with film-forming materials. Another object is to provide a new method of mixing various additives, and in particular coloring components, with the film-forming material. A still further object is to. provide an apparatus and process for the manufacture of colored film wherein the color is intimately dispersed within the film. Still another object is to produce a colored film product which is relatively free of comb lines, herring bone lines and the like defects. Still a further object is to produce a colored film of the type indicated, which film is particularly adapted to receive a light-sensitive coating, thereby yielding a photographic product having improved properties. Other objects will appear hereinafter. Y.

2,972,546 Patented Feb. 21, 1961 We have found that if a relatively dilute solution or dispersion of the additive material, such as a dilute solution of an organic dye, is introduced into the film-forming dope in a certain manner in our novel apparatus as will be described in detail hereinafter, that a modified film of excellent quality may be obtained in a rapid and improved manner. In our novel process and apparatus the additive, such as a dye solution, is introduced shortly before the film-forming operation thereby contaminating only a small portion of the apparatus arrangement with the coloring material. Accordingly, in our invention it is relatively easy to change from one color to another color and apparatus cleaning is kept to a minimum.

For a more complete understanding of our invention, reference will be made to the attached drawings forming a part of the present application.

In the attached drawings Figure 1 is a diagrammatic flow sheet type of illustration of an overall arrangement of apparatus in accordance with the present invention for making colored film.

Figure 2 is a semi-diagrammatic side elevation view showing in more detail our new injector-blender of the present invention, which unit is diagrammatically represented at A in Figure 1. Referring to Figure 1, 10 represents a tank or other similar container in which the film-forming materials are prepared and put into solution. For example, 10 may comprise a conventional chemical mixer in which the film-forming ingredients are distributed into a suitable solvent. That is, in this container cellulose acetate could be dissolved in a solvent such as acetone (for cellulose acetate having an acetyl below 40%) or in a halogenated hydrocarbon solvent such as methylene chloride (for cellulose acetate having an acetyl content in the range of 42% to 44%).

The container 10 is connected by pipe 11 to a further tank 12 designated holding and circulating mixer. This tank 12 may likewise be a piece of conventional chemical equipment made up of stainless steel and provided With suitable stirring devices therein.

From one side of tank 12 there is provided an outlet line 13 which feeds the several branch lines 14, 15, 16, and 17. After feeding the last branch line 17, the conduit returns as at 18 to tank 12. By this arrangement the film-forming dope may be circulated around the system constantly and portions thereon drawn off at the several lines 14, 15, etc., as needed. Suitable pumps and metering devices (not shown) may be incorporated in the system as desired for circulating the dope and measuring the flow.

Referring now to the branch lines 14, 15, 16, and 17, these lines lead to injector-blenders, designated overall as A and numbered 18, 19, 20 and 21. These injectorblenders are shown in detail in Figure 2, and will be described further below. However, it will be noted that the film-forming materials are fed upwardly into the blender at points 22, 23,. 24, and 25. Also leading into the lower part of the blender for upward feeding are the lines 26, 27, 28 and 29 through which the additive such as a dye solution may be incorporated.

At the upper part of the blenders there are provided draw-0E lines 31, 32, 33, and 34 which lead, for example, to the casting machine in which the film may be formed. The film-forming machine may be of any type. Hence, description of film-forming mechanism in the present application is unnecessary. It appears sufiicient to mention that film-forming equipment with associated drying chambers such as shown in Fordyce et al. US. Patents Nos. 2,319,051-2,319,055 may be used.

Referring now to Figure 2, this shows on a larger scale the unit designated overall as A in Figure 1. This unit is made up of a cylindrical shell 41 which may be in two parts. That is, provision may be made at 42 for bolting or clamping two sections together for forming the unit thereby permitting disassembly of the unit for repair or cleaning. Gaskets can be inserted at such joints.

On the upper portion of the unit there is positioned amotor 43. This motor drives a shaft 44 which carries a plurality of agitator blades 45 and 46. The shaft 44 extends through a suitable seal as at 47 whereby the contents within unit 41 are prevented from passing up the shaft into the motor. The lower part of apparatus 41 is provided with an enlarged inlet means 48. This inlet is adapted to be connected with the lines such as 14, 15, etc. shown in Figure 1 so that the film dope may be passed into the bottom of apparatus 41 and upwardly therethrough.

Also leading into the bottom of 41 is a conduit 49 which conduit is suitably angled as at 51 so that the discharge therefrom takes place as at 52. The position of the discharge is on the periphery of the mixer blades which we have found is the zone of highest mixing velocity, thereby enab ing the best incorporation of the additive into the dope.

The lower portion of conduit 49 is connected by conduit 52 through a suitable pump 53 to a container 54 which contains the additive such as a dye solution which it is desired to incorporate in the dope.

Returning now to a consideration of the interior of the injector-blender 41, as already mentioned by the discharge of the additive at point 52, namely in the periphery Zone of the mixer blades, the passage of the dope and the additive upwardly through the zone permits the obtaining of excellent dispersion of the additive, such as' a dye solution, into the dope. In addition, by the passage upwardly of the components through the apparatus any heavy particles tend by gravity to be delayed somewhat in their passage through our injector-blender. By the centrifugal force produced by the rapidly rotating blades 45 and 26, any delayed particles would be thrown to the outside walls thereby breaking them up and dispersing them into the mixture.

The ingredients, after complete mixing as just described, are discharged through discharge conduit 56 positioned in the upper part of the unit. This discharge conduit 56 connects with conduit 31 or 32, etc. of Figure 1 and leads to a suitable film casting device such as shown in the Fordyce et al. Patents Nos. 2,3l9,05l2,319,055 already mentioned above.

The operation of the above apparatus described with respect to Figures 1 and 2 is believed understandable to a substantial extent from the description already set forth. However, the following further description will further illustrate the operation of our new apparatus arrangement. As already pointed out, the present apparatus is designed to facilitate the production of colored sheeting. The sheeting, while particularly adapted for use as a film base for carrying a light-sensitive emulsion, may be used for various other purposes such as safelights, packaging material, decorating purposes and the like. The additive which we prefer to use for incorporating in the film dope is usually a relatively dilute solution of certain organic dyes. However, as will be apparent from certain of the examples which follow, certain other additives may be incorporated by the instant apparatus. In general it is desirable that the additive whether it be a dye solution or some other material, not cause a detrimental change in the casting or curing properties of the resultant sheet of film made from the dope having the additive incorporated therein.

In addition, the additive preferably should be relatively noncorrosive. However, this limit has been extended by the utilization of relatively dilute solutions of the additive. Also since the dope containing the additive only contacts a relatively small portion of the overall equipment in use, this portion of the equipment can be made of special corrosion-resistant materials such as special stainless steels, if a corrosive additive is to be en1 ployed. It is not only possible to use dispersed dyes but other varieties such as spirit soluble, oil, acid, basic and vat dyes that are soluble in suitable solvents may be employed. The procedure of using relatively dilute solutions of the dye and injecting such dyes in the injector-blender described in detail above eliminates crocking and greatly enhances the quantity of colors that can be obtained in the final product.

The operation of our apparatus and process will be further apparent from the several examples which follow. These examples will illustrate the type of film-forming solution which may be fed into our injector-blender at inlet 43 and the types of additive and the amount thereof which may be fed into conduit 49 so that the additive discharges in the periphery zone aforementioned.

Injection of these solutions upwardly into the mixer occurs at the following relative ratios 00.75% of Solution B into Solution A; the resulting solution is then cast into a sheet to give a final thickness of 00.725.

Example 11 Solution A is the mixture of the following two ball milled dispersions:

(1) Titanium dioxide pounds 333.3 Cellulose acetate butyrate do 33.3 Plasticizer do 16.6 Ethylene dichloride do 554 Methanol do 62 (2) Iron blue .do 10 Plasticizer do 60 Solution B:

Triphenyl phosphate parts .3

Cellulose triacetate do 1.0

Methylene chloride do 5.0

Methanol do .5

These solutions are mixed by injection at the rate of 2% Solution A, 98% Solution B.

This resulting solution is cast at a thickness to give a final sheet thickness of 0.005".

Example III Solution A (ball milled): Parts Titanium dioxide 30.3 Cellulose acetate butyrate 3.3 Plasticizer 1.7 Ethylene dichloride 55.4 Methanol 6.2 Dye of the formula below 3 Solution A is injected upwardly into the mixer at the rate of 2% of Solution B. The resulting dope is then cast at the desired thickness.

Example IV Solution A: Parts Diisooctyl phthalate 1 Methylene dichloride .9 Methanol .1

Solution B:

Cellulose triacetate 1 Methylene dichloride 5.0 Methanol .5

Solution A is injected into Solution B at the rate of 3.3%.

Example V Solution A (ball milled): Titanium dioxide ...percent Cellulose acetate butyrate do 3 Methanol do 7 Ethylene dichloride do. 60

Solution B:

Cellulose triacetate parts 1 Methylene dichloride do 5.0 Plasticizer do .3 Methanol dn ,5 40 Solution A is injected at the rate of 5% into Solution B.

Example VI Solution A:

Cellulose acetate parts 1 Plasticizer do .3 Acetone do 3-4 Methanol do .3.4

Solution B:

Azosol Fast Blue BLA ....percent .08 Acetone do 92.00 Methanol do 7.92 Solution B is injected at the rate of .25% into Solution A and is cast into sheets to give a thickness of .003 inch to 0.010.

Certain of the colored film base produced as described above was coated with a light-sensitive emulsion. For example, certain of the film base produced in accordance with Example I was coated with an emulsion to make X-ray film. It was found that the film upon exposure and processing gave very excellent radiographs. The tinting of the film base as accomplished by the present invention gave a product which was extremely uniform in color and was free of comb lines and the like.

Certain of the colored sheeting prepared as above described had applied thereto a colorless adhesive. That is, certain of the commercially available Vinylite adhesives may be used. There was then laminated to the adhesive a very thin metallic sheet or foil. For example, aluminum or gold foil may be so laminated to the colored sheeting. This produced a colored sheet of excellent metallic lustre. Such sheet may be used for wrapping materials or cut up into strands which are twisted to make metalized yarn. Such laminated sheet made up of a colored plastic sheet laminated to the metal with a colorless adhesive is more uniform and otherwise represents an improvement over comparable products heretofore produced by using an uncolored sheet laminated with a colored adhesive.

It is believed apparent from the foregoing that we have provided an improved apparatus and method for making sheet or film containing an additive, particularly an additive which imparts a color or tint to the sheeting. The sheeting produced by the apparatus and method of the present invention not only is particularly adapted for use as photographic film base where a colored or tinted base is desired, but the colored sheets may be used in various other ways.

We claim:

1. In a process of manufacturing colored film by a procedure which includes substantially continuously circulating in a closed circuit film-forming materials and a solvent therefor, withdrawing from the circuit at a plurality of said points the film-forming material with its solvent and introducing coloring materials in the withdrawn portions, the improvement features which comprise passing the withdrawn materials upwardly through a zone of agitation, substantially simultaneously also injecting upwardly and into intimate contact with said film-forming materials a solution of said coloring materials, said coloring materials being introduced into said zone of agitation in the vicinity of the periphery thereof whereby intimate mixing of the coloring materials with the film-forming materials is obtained and withdrawing the film-forming materials which have been thus colored from the process at a point above the point of introduction.

2. A process in accordance with claim 1 wherein the coloring materials comprise a dilute solution of not more than 1% of the coloring ingredients in at least 99% solvent.

3. A process is accordance with claim 1 wherein the film-forming materials and solvent therefor constitute at least 98% and the coloring material and its solvent constitute not more than 2%, said percentages being by weight.

4. A process in accordance with claim 1 wherein the film-forming materials comprise cellulose triacetate and triphenyl phosphate dissolved in methylene chloride and methanol.

5. A process in accordance with claim 1 wherein the coloring materials include a dye having the formula 0 OH H OH NO: 6 NQCHzCHzOH 6. A process in accordance with claim 1 wherein the coloring materials include a dye having the formula References Cited in the file of this patent UNITED STATES PATENTS 1,720,573 Roberts July 9, 1929 1,983,520 Charch et al Dec. 11, 1934 2,039,708 Crouch et al. May 5, 1936 2,185,649 Ruofi Jan. 2, 1940 (Other references on following page) 7 8 UNITED STATES PATENTS 2,516,844 Kyame Aug. 1, 1950 2,290,952 Ellis et a1. July 28, 1942 2,559,518 Srmth July 3, 1951 2,343,928 Roberts "Mar, 14, 1944 2,608,392 Bowman ,4 g- 26, 1952 2,383,995 Stanley et a1. Sept. 4, 1945 2,626,786 McGlothlin 2 19 3 2,393,652 Olpin e161. Jan. 29, 1946 5 2,644,814 Fischer July 7, 1953 2,469,416 Smyers May 10, 1949 2,650,168 Van Dijk et a1 Aug. 25, 1953 2,497,346 Collins Feb. 14, 1950 2,661,299 Paul et a1. Dec. 1, 1953 

1. IN A PROCESS OF MANUFACTURING COLORED FILM BY A PROCEDURE WHICH INCLUDES SUBSTANTIALLY CONTINUOUSLY CIRCULATING IN A CLOSED CIRCUIT FILM-FORMING MATERIALS AND A SOLVENT THEREFOR, WITHDRAWING FROM THE CIRCUIT AT A PLURALITY OF SAID POINTS THE FILM-FORMING MATERIAL WITH ITS SOLVENT AND INTRODUCING COLORING MATERIALS IN THE WITHDRAWN PORTIONS, THE IMPROVEMENT FEATURES WHICH COMPRISE PASSING THE WITHDRAWN MATERIALS UPWARDLY THROUGH A ZONE OF AGITATION, SUBSTANTIALLY SIMULTANEOUSLY ALSO INJECTING UPWARDLY AND INTO INTIMATE CONTACT WITH SAID FILM-FORMING MATERIALS A SOLUTION OF SAID COLORING MATERIALS, SAID COLORING MATERIALS BEING INTRODUCED INTO SAID ZONE OF AGITATION IN THE VICINITY OF THE PERIPHERY THEREOF WHEREBY INTIMATE MIXING OF THE COLORING MATERIALS WITH THE FILM-FORMING MATERIALS IS OBTAINED AND WITHDRAWING THE FILM-FORMING MATERIALS WHICH HAVE BEEN THUS COLORED FROM THE PROCESS AT A POINT ABOVE THE POINT OF INTRODUCTION. 